2-Trifluoromethylimino-benzo-heterocyclic compounds

ABSTRACT

2-TRIFLUOROMETHYLIMINO-BENZO-HETEROCYCLIC COMPOUNDS OF THE GENERAL FORMULA   IN WHICH X is oxygen or sulfur, Y is oxygen, sulfur or the radical   R is a lower alkyl, cycloalkyl, aryl, aryl substituted by at least one of halogen, nitro, methyl and methoxy, alkylcarbalkoxy with up to 6 carbon atoms, alkysulfonyl, arylsulfonyl, dialkylamidosulfonyl, or -CO-R&#39;&#39;, R&#39;&#39; is alkyl or alkoxy with up to 12 carbon atoms, aryl, amino, lower alkylamino, di-lower alkylamino, or arylamino, EACH Z independently is halogen, trifluoromethyl, nitro, lower alkyl, lower alkoxy, di-lower alkylamino, acyl with up to 6 carbon atoms, a sulfonic acid group, a sulfonic acid amide group, or a sulfonic acid amide group substituted by alkyl with up to 6 carbon atoms, and M IS AN INTEGER FROM 0 TO 4, WHERE POSSESS FUNGICIDAL, INSECTICIDAL AND ACARICIDAL PROPERTIES, AND A PROCESS FOR THEIR PREPARATION WHEREIN A COMPOUND OF THE GENERAL FORMULA   IS REACTED WITH PERFLUOROAZAPROPENE OF THE FORMULA

United States Patent 91 Buttner et al.

[ 1 May 20, 1975 22 Filed: Mar. 26, 1973 211 Appl. No.: 344,800

[30] Foreign Application Priority Data Apr. 15, 1972 Germany 2218329 [52] US. Cl 260/307 D; 260/305; 260/327 M;

[51] Int. Cl C07d 85/48 [58] Field of Search 260/305, 307 D [56] References Cited UNITED STATES PATENTS 2,851,391 9/1958 Gevjovich et al 167/33 3,770,769 11/1973 Schneider 260/327 M Primary Examiner-Donald G. Daus Assistant Examiner-Raymond V. Rush Attorney, Agent, or FirmBurgess, Dinklage & Sprung [5 7 ABSTRACT 2-trifluoromethylimino-benzo-heterocyclic pounds of the general formula 1: Z -@i -CF ,(I) m .3 I 1 comin which X is oxygen oi sulfur, Y is oxygen, sulfur or the radical R is a lower alkyl, cycloalkyl, aryl, aryl substituted by at least one of halogen, nitro, methyl and methoxy, alkylcarbalkoxy with up to 6 carbon atoms, alkysulfonyl, arylsulfonyl, dialkylamidosulfonyl, or CO-R',

R is alkyl or alkoxy with up to 12 carbon atoms, aryl, amino, lower alkylamino, di-lower alkylamino, or arylamino,

each Z independently is halogen, trifluoromethyl, nitro, lower alkyl, lower alkoxy, di-lower alkylamino, acyl with up to 6 carbon atoms, a

sulfonic acid group, a sulfonic acid amide group, i

or a sulfonic acid amide group substituted by alkyl with up to 6 carbon atoms, and m is an integer from 0 to 4,

where possess fungicidal, insecticidal and acaricidal properties, and aprocess for their preparation wherein a compound of the general formula is reacted with perfluoroazapropene of the formula r w-cs in an aprotic solvent in the presence of a hydrogen fluoride acceptor. 1

7- Claims, No Drawings Z-TRIFLUOROMETHYLIMINO-BENZO- HETEROCYCLIC COMPOUNDS The present invention relates to and has for its objects the provision of particular new 2- trifluoromethylimino-benzo-heterocyclic compounds which possess fungicidal, insecticidal and acaricidal properties, active compositions in the form of mixtures of such compounds with solid and liquid dispersible carrier vehicles, and methods for producing such compounds and for using such compounds in a new way especially for combating pests, e.g. fungi, insects and acarids, with other and further objects becoming apparent from a study of the within specification and accompanying examples.

2-Trifluoromethylimino derivatives of heterocyclic five-membered rings with a fused benzene nucleus have not hitherto been disclosed.

The present invention provides 2- trifluoromethylimino derivatives of heterocyclic compounds with five-membered rings, of the general formula in which X is oxygen or sulfur, Y is oxygen, sulfur or the radical R is lower alkyl, cycloalkyl; aryl, aryl substituted by at least one of halogen, nitro, methyl and methoxy, alkylcarbalkoxy with up to 6 carbon atoms, alkylsulfonyl, arylsulfonyl, dialkylamidosulfonyl, or CO-R',

R is alkyl or alkoxy with up to 12 carbon atoms, aryl,

Z preferably is chlorine, trifiuoromethyl, nitro, alkyl with up to 4 carbon atoms, the sulfonic acid group or the sulfonamido, N-methyl-sulfonamido or N,N- dimethylsulfonamido radical. Preferably m is 0, l, 2 or 4.

The invention also provides a process for the production of a compound of formula (I) in which a compound of the general formula YH (II) in which X, Y. Z and m have the abovementioned meanings,

is reacted with perfluoroazapropene of the formula F C=N'-CF (III) five-membered rings of the formula (I). It is further- 1 more surprising that the compounds according to the amino, lower alkylamino, di-lower alkylamino, or

arylamino,

each Z independently is halogen, trifluoromethyl, ni-

tro, lower alkyl, lower alkoxy, di-lower alkylamino, acyl with up to 6 carbon atoms, a sulfonic acid group, a sulfonic acid amide group, or a sulfonic acid amide group substituted by alkyl with up to 6 carbon atoms, and

m is an integer from 0 to 4.-

When Y is R preferably is methyl, ethyl, cyclohexyl, phenyl, chlorophenyl, nitro-phenyl or lower alkylcarbo-lower alkoxy with up to 4 carbon atoms in each alkyl group, or methanesulfonyl, ethanesulfonyl, p-toluene-sulfonyl or dimethylamidosulfonyl, or the acyl group CO-R', wherein R is alkyl or alkoxy with up to 8 carbon atoms, or phenyl, lower alkylamino or di-lower alkylamino, each with up to 4 carbon atoms in each alkyl moiety.

invention possessfungicidal, acaricidal and insecticidal activity. A technical advance has been achieved by the discovery of this new category of compounds having interesting properties, and of the unusual process for their production.

It is noteworthy that in formula (II) even if Y is NR- X cannot also be -NR-, i.e., the starting material cannot be an'o-phenylenediamine. Such diamines do not react in the same way, i. e. they do not undergo ring closure in accordance with the present invention. Furthermore, they are unstable in the presence of acids and undergo polymerization;

If o-(N-acetyD-aminophenol and perfluoroazapropene are used as the starting compounds and sodium fluoride as the acid binding agent, the course of the rev n e-(i=0 I) 'NCF 2 5'5 I 11 0-0 0 The compounds of the formula (II) to be used as starting substances are known and may be prepared according to a known process as described for example Helvetica Chim. Acta 22, 92 (1939); US. Patent Specification 2,795,610; J. Amer. Chem. Soc. 51,

butylpyrocatechol; perchloropyrocatechol; ophenylenedithiol; perchlorophenylenedithiol;

4-methyl-o-phenylenedithiol, 'o-(N-methyl-amino)- thiophenol; 5-nitro-2-(methyl-amino )-thiopheno1, o- (N-methylamino)-phenol; 5-chloro-2-(N- methylamino)-phenol, o-(N-phenvlamino)-ohenol: o- (N-2 ,4-dinitrophenylamino)-phenol; 4-chloro-2-( N- carbethoxymethyl)-aminophenol; o-(N-acetyl)- aminophenol; 4-methyl-2-(N-acetylamino)-phenol; 2- (N-acetyl-amino)-4-(methylamino-sulfonyl)-phenol;

o-(N-benzoyl)-aminophenol; o-[N-(2,5- dichlorobenzoyl)]-aminophenol; o-[N-(3-trifluoromethylbenzoyl)]-aminophenol; o-[N-(4-tert.-butylbenzoyl)]-aminophenol, o-( N-carbomcthoxy)- aminophenol; 3,5-dichloro-2-(N-carbethoxy)- aminophenol; 4-nitro-6-chloro-2-( N-carbomethoxy aminophenyl; o-( N-dimethylaminocarbonyl aminophenol; 4-chloro-5-nitro -2-(N-dimethylaminocarbonyl)-aminophenol; 4-nitro-2-( N- methylaminocarbonyl)-aminophenol; 4-nitro-2-[N-(nbutylaminocarbonyl)]-aminophenol; 4-chloro-2-(N- methylaminocarbonyl)-aminophenol; o-(N-methyl sulfonyl)-aminophenyl, o-[N-(n-butyl sulfonyl)]- aminophenol; 4-acetyl-2-(ethylsulfonyl)-aminophenol; o-(N-tosyl)-aminophenol; o-[N-(3-nitro-phenyl sulfonyl)]-aminophenol; o-[N-(3'-chloro- 4methylphenylsulfonyl)]-aminophenol; and o-(N- dimethylaminosulfonyl)-aminophenol.

The perfluoroazapropene of the formula (III) to be used as a starting substance is also known, being disclosed in Chem. Review 65, 387 (1965) and J. Chem. Ing. Data 10, 398 (1965)).

As solvents it is generally possible to-use aprotic substances such as chlorinated hydrocarbons, for example methylene chloride, chloroform o'r chlorobenzene, or aromatic hydrocarbons, for example benzene or toluene), but preferably dipolar aproticsolvents such as acetonitrile, acetone, dimethylformamide, sulfolane and dimethylsulfoxide. An aprotic solvent is defined as a diluent which does not contain an ionizable proton in the molecule.

(Rompp, Chmie-Lexikon, page 217, Francksche Verlagsbuchhandlung, Stuttgart (1972), and also Chem. Review 69, page 1-32 (1969)).

As acceptor for the hydrogen fluoride produced in the reaction it is possible to use a tertiary amine, such as triethylamine or dimethylaniline, but it is preferred to use an alkali metal fluoride, such as sodium fluoride or potassium fluoride.

The reaction temperatures can be varied over a wide range. In general, the reaction is carried out at about 0 to 100C, preferably at about to 80C.

The process according to the invention can for example be carried out by dissolving a molar equivalent of 5 the starting material of formula (II) in acetonitrile, dimethylformamide or toluene, adding about 2 molar equivalents of dry sodium fluoride, and progressively introducing about 1 to 1.5 molar equivalents, preferably about 1.2 molar equivalents, of perfluoroazapropene, for example from a steel cylinder, into the resulting suspension, in the temperature range indicated above, while stirring. After completion of the reaction, the mixture may be stirred further for a short time, the precipitated sodium hydrogen fluoride may be filtered off and the solvent may be concentrated in vacuo. The crystalline crude product which remains is in many cases sufficiently pure, or it can be easily purified by recrystallization.

According to a special embodiment of the invention it is possible to use the perfluoroazapropene (III), in

the form of an addition product thereof, namely bis- (trifluoromethyl)-amine (IV) which maybe produced by addition of hydrogen fluoride to (I11), and N,N,N'- tris-(trifluoromethyl)-fluoroformamidine (V), which may be produced by dimerization-of (III), i.e. addition to itself. The process can in this way be carried out more easily because preparation of pure perfluoroazapropene can be dispensed withand because the compounds mentioned, of the respective formulae can be added dropwise as liquids, because of their higher boiling points.

The active compounds according to the invention display a' strong fungitoxic action. They do not appear to harm crop plants in the concentrations required to combat fungi, and they have a low toxicity to warmblooded animals. For these reasons they are suitable for use as plant protection agents for combating fungi. Fungitoxic agents are employed in plant protection for combating Archimycetes, Phycomycetes, Ascomycetes, Basidiomycetes and Fungi Imperfecti.

The active compounds according to the invention have a broad spectrum of action and can be employed against parasitic fungi which attack above-ground parts of plants, or attack the plants through the soil, and also against seedborne causative organisms of diseases.

The compounds possess a good action against F usicladium dendriticum, the causative organism of apple scab, against Podosphaera leucotricha, the causative organism of powdery mildew of apples, against Helminthosporium gramineum, the causative organism of stripe disease of barley, and against Tilletia caries, the causative organism of bunt of wheat.

However, the compounds according to the invention arev also active against other fungi which attack rise plants or other crop plants, such as Mycosphaerella musicola, Verticillium alboatrum, Phialophora cinerescens and varieties of Fusarium.

The compounds according to the invention are distinguished by a good activity and a broad spectrum of action against phytopathogenic soil fungi and against seed-borne fungal diseases of plants. They can suitably be used as soil treatment agents and seed dressings, and are in many cases superior to customary commercially available preparations. 4

The compounds according to the invention furthermore possess an insecticidal and acaricidal activity. They may be successfully employed in plant protection for combating harmful sucking and biting insects, Diptera and mites (Acarina), also in the veterinary and hygiene fields, and furthermore in the protection of stored products against a large number of animal pests (endoparasites and ectoparasites).

To the sucking insects there belong, in the main, aphids (Aphidae) such'as the green peach aphid (Myzus persicae), the bean aphid (Doralis fabae), the bird cherry aphid (Rhopalosiphum padi), the pea aphid (Macrosiphum pin) and the potato aphid (Macrosiphum solizn ifolii), the currant gall aphid (Cryptomyzus peridum)-as well as the grape mealybug (Pseudococcus maritimus); thrips (Thysanoptera), such as Hereinathrips femoralis, and bugs, for example the beet bug, (Piesma quadrata), the red cotton bug (Dysdercus iniermedius), the bed bug (Cimex lectularius), the assassin bug (Rhodnius prolixus) and Chagas bug (Triatoma irifestans) and, further, cicadas, such as Euscelis bilobatus and Nephotettix bipunctams.

In the case of the biting insects, above all there should be mentioned butterfly caterpillars (Lepidoptera) such as the diamond-back moth (PIuteIIa maculipennis), the gypsy moth (Lymantria dispar), the browntail moth (Euproczis chrysorrhoemand tent caterpillar (Malacosoma neustria); further, the cabbage moth (Mamestra brassicae) and the cutworm (Agmtis sage tum), the large white butterfly (Pieris hrassicae), the small winter moth (Cheimatohia brumala), the green oak tortrix moth (Torrrix viridana), the fall armyworm (Laphygma frugiperda) and cotton worm (Prodenia litura), the ermine moth (Hyponomeuta padella), the Mediterranean flour moth (Ephestia kuhniella) and greater wax moth (Galleria mellonella).

With the mites (Acari) there are classed, in particw lar, the spider mites (Tetranychidae) such as the twospotted spider mite (Tetranychus urticae) and the European red mite (Paratetranychus pil0sus-= Panonychus ulmi), gall mites, for example the blackcurrant gall mite (Eriophyes ribis) and tarsonemids, for example the broad mite (Hemitarsonemus latus) and the cyclamen mite (Tarsonemus pallidus); finally, ticks, such as the relapsing fever tick (Ornithodorus moubata).

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders, i.e. diluents, carriers or extenders of the type usable in conventional pesticide formulations or compositions, e.g. conventional pesticide dispersible carrier vehicles such as gases, solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compounds with conventional pesticide dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g. conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: aerosol propellants which are gaseous at normal temperatures and pressures, such as freon; inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, alkyl naphthalenes, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc.), cycloalkanes (e.g. cyclohexane, etc.), paraffins (e.g. petroleum or mineral oil fractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride, chloroethylenes, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, glycol, etc.) as well as ethers and esters thereof (e.g. glycol monomethyl ether, etc.), amines (e.g. ethanolamine, etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sulfoxide, etc.), acetonitrile, ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, clays,

alimina, silica, chalk, i.e. calcium-carbonate, talc, attapulgite, montmorillonite, kieselguhr, etc.) and ground synthetic minerals (e. g. highly dispersed silicic acid,- silicates, e.g.-alkali silicates, etc,); whereas the following may be chiefly considered for use as conventional car,- rier vehicle assistants, e.g. surface-active agents, for this purpose: emulsifying agents, such as non-ionic and- /or anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfates, alkyl sulfonates,'aryl sulfonates, albumin hydrolyzates, etc., and especially alkyl arylpolyglycol' ethers, magnesium stearate, sodium oleate, etc.);' and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid, and/orliquid dispersible carrier vehicles and/or with other known compatible active agents, "especially plant protection agents, such as other fungicides, insecticides and 'aca ricides, or rodenticides, nematocides, herbicides, fertilizers, growth-regulating agents,'etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes and granules, which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 01-95 percent by weight, and preferably 0.5- percent by weight, of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.0001-10 percent, preferably 0.01-1 percent, by weight of the mixture. Thus, the present invention contemplates over-all compositions which comprises mixtures of a conventional dispersible carrier vehicle such as (l) a dispersible inert finely divided carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/or water preferably including a surface-active effective amount of a carrier vehicle assistant, e.g. a surface-active agent, such as an emulsifying agent and- /or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.0001- percent, and preferably 0.01-95 percent, by weight of the mixture.

The active compounds can also be used in accordance with the well known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment, in finely divided form, e.g. average particle diameter of from 50-100 microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about 15 to l 000 g/hectare, preferably 40 to 600 g/hectare, are sufficient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about 20 to about 95 percent by weight of the active compound or even the percent active substance along, eg about 20-100 percent by weight of the active compound.

For soil treatment, amounts of active compound of l to 500 g per m of soil, preferably 10 to 200 g, are generally required.

In the treatment of seed, amounts of active compound of 0.01 to 50 g per kg of seed, preferably 0.1 to g', arein general required. for application as seed dressings.

Furthermore, the present invention contemplates methods of selectively killing, combating or controlling pests, e.g. fungi, insects and acarids, which comprises applying to at least one of correspondingly (a) such fungi, (b) such insects, (c) such acarids, and (d) the correspondingly habitat thereof, i.e. the locus to be protected, a correspondingly combative or toxic amount, i.e. a fungicidally, insecticidally or acaricidally effective amount, of the particular active compount of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, squirting, sprinkling, pouring, fumigating, and the like.

It will be realized, of course, that the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.

Active compound ooc The synthesis, unexpected superiority and outstanding activity of the particular new compounds of the 60 present invention are illustrated, without limitation, by

the following examples:

EXAMPLE 1 i Podosphaera test (powdery mildew of apples) [Protective Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylarylpolyglycol ether sired concentration of the active compound in the spray liquid was mixed with the stated amount of solvent, and the concentrate was diluted with the stated amount of water which contained the stated additions.

Young apple seedlings in the 4 6 leaf stage were sprayed with the spray liquid until dripping wet. The plants remained in a greenhouse for 24 hours at 20C and at a relative atmospheric humidity of 70 percent.

They were then inoculated by dusting with conidia of the apple powdery mildew causative organism (Podosphaera leucotricha Salm.) and placed in a greenhouse at a temperature of 21 23C and at a relative atmospheric humidity of about 70 percent.

Ten days after the inoculation, the infection of the seedlings was determined as a percentage of the untreated but also inoculated control plants.

0 percent means no infection: 100 percent means that the infection was exactly as great as in the case of the control plants.

The active compounds, the concentrations of the ace, tive compounds and the results can be seen from the 25 following Table: i

able 1 Podoeghaera test /protective Infection in 7 of the infection of the untreated control at on active compound concentration (in f by weight) of 3 u- -s-s-'sn 29,

EXAMPLE 2 Fusicladium test (apple scab) Protective I Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether Water: parts by weight v The amount of active compound required for the de sired concentration of the active compound in the spray liquid was mixed with the stated amount .of solent, and the concentrate was diluted with the stated amount of water which contained the stated additions.

Young apple seedlings in the 4 6 leaf stage were sprayed with the spray liquid until dripping wet. The plants remained in a greenhouse for 24 hours at 20C and at a relative atmospheric humidity of 70 percent. They were then inoculated with an aqueous conidium suspension of the apple scab causative organism (F usicladium dendriricum el) and incubated for 18 hours in a humidity chamber at 18 20C and at a relative atmospheric humidity of 100 percent.

The plants then again came into a greenhouse for 14 Active compound days.

15 days after inoculation, the infection of the seedlings was determined as a percentage of the untreated 5 but also inoculated control plants.

The active compounds, the concentrations of the active compounds and the results can be seen from the following table:

Table 2 Fusicladium test/protective Infection in 95 of the infection of the untreated control at an active compound concentration (in by weight) of CH CH 3 N-s-s-s-g-n 3 31 CH3 8 CH3 (known) (A) @N m-cF m 1 Agar plate test Test for fungitoxi activity spectrum.

Solvent: Acetone Parts by weight: a) 1,000 b) 100 To produce a suitable preparation of the active compound, 1 part by weight of the active compound was taken up in the stated amount of solvent.

The preparation of the active compound was added to potato dextrose agar (which has been liquefied by heating) in such an amount that the desired concentration of active compound was set up therein. After thorough shaking to achieve a uniform dispersion of the active compound, the agar was poured into Petri dishes under sterile conditions. When the mixture of substrate c effectiveness and breadth of the and active compound had solidified, test fungi from pure cultures were inoculated onto it in small discs of 5 mm diameter. The Petri dishes remained at 20C for I 3 days for incubation.

After this time, the inhibiting action of the active compound on the mycelium growth was determined in categories, taking into account the untreated control. 0 means'no mycelium growth, either on the treated substrate or on the inoculum; the symbol meansmycelium growth on the inoculum only, no spread to the treated substrate; and the symbol means mycelium growth from the inoculum onto the treated substrate, similar to the spread to the untreated substrate of the control.

The active compounds, the concentration of the active compounds, the test fungi and the inhibition effects achieved can be seen from the following table:

Table3 Agar plate test d m g g 9 Active compound Active compound 5 "a 2 g a ,3 5

concentration in H g H 2 g g 5 5 H 5 the substrate,.in o oz 3 OS no a mgperlitre E g .20 Pg 8 3m g fl 8883 01 m8 0 at; 8

Untreated- S cH2"m1-&.S\ Zn a; 10 b 100 0 O 0 S (known) (A) a; 10 '0 o o o o o o o =u-cr (5) b 100 o o o o o o o o 0 3 (on c 0 v 3 3 10 o o o o o (Dir- 3 b 100 o o o o o o a) 10 o o o 0 o o o 0 K 1: 100 o o o o o o o o (INA-PF: 2)

I C0-C8:

a; '10 o o o o b 100 O O 0 O O O O Q H 0P 3 o-cu (11) 158 o o O H 0 O O O O O O H 01 coo-cu (14) EXAMPLE 4 Seed dressing test/bunt of wheat (seed-borne mycosis) To produce a suitable drydressing, the active compound was extended with a mixture of equal parts by weight of talc and kieselguhr to give a finely'powdered mixture with the desired concentration of the active compound. v

Wheat seed was contaminated with 5 g of the chlamydospores of .Tilletia caries per kg of seed. To apply the dressing, the seed was shaken with the dressing in a closed glass flask. The seed, on moist loam under a cover of a layer of muslin and 2 cm of moderately moist compost soil, was exposed to optimum germination conditions for the spores for days at 10C in a refrigerator.

The germination of the spores on the wheat grains, each of which was contaminated with about 100,000

spores, was subsequently determined microscopically.

ing used and the percentage spore germination can be seen from the following Table:

To produce a suitable dry dressing, the active compoundwas extended with a mixture of equal parts by weightof talc and kieselguhr to give a finely powdered mixture with the desired concentration of active compound. j I

To apply the dressing, barley seed, which was naturally infected byv Helminthosporir m gramineum, was

shaken with the dressing in a closed glass flask. The

seed, on moist filter paper discs in closed Petri dishes, was exposed to a temperature of 4C for 10 days in a refrigerator. The germination of the barley, and possibly also of the fungus spores, was thereby initiated. Two batches of grains of the pregerminated barley were subsequently sown 2 cm deep in Fruhstorfer standard soil and cultivated in a greenhouse at temperatures of about 18C in seed boxes which were exposed to light for 16 hours daily. The typical symptoms of the stripedisease developed within 3 to 4 weeks.

The active compounds, the concentration of the ac- Table 4 Amount of Active compound Active compound dpoge germination concentration in dressing used in I the dressing, in in g/kg of by weight p seed without dressing v i 10 I v S i II 43.0.3 7 v. CH2 zn 1o '1 5 -mt-c-s CH2 I CH (11 co-cu '0" =ucr (15) 1o 2' 0.005

/ O 0C H EXAMPLE 5 tive compounds in the dressing, the amounts of dress- Seed dressing test/stripe disease of barley (seed-borne mycosis) ing used and the number of diseased plants can be seen from the following Table:

Seed dressing test/stripe diseaseof barley Active compound Actiye compound concentration in Number of plants Amount of dressing with stripe disease,

.used', in g/kg of the dressing, in seed in 7": of the total 73 by weight number of emerged plants without dressing v 41.3

S on 411-5: s

2 v Zn 3o 2 38.1 ca -rm-o-s 30 2 o o O: f

crew 30 2 4.1 3 (11) (IO-CH EXAMPLE 6 30 These'bean plants were heavily infested with the two- 1 spotted spider mite or bean spider mite (Tetranychus urticae) in all stages of development.

After the specified periods of time, the effectiveness I killed. I

The active compounds; the concentrations of the'ac tive compounds, the evaluation times and the results can be seen from the following Table:

liable 6 Tetrgzchus test, resistant Tetrgxchus test, resistant Active compounds A Active com- Degree of poun'd condestruccentration t-ion in 5% in 7 by after 2v j weight days O\ @[N QICFB (16) 0.1 '100 O lI(OH I 0 @K =1sIcF 0.1 100 N 0.01 c1 I I O=C-I I-OH (19) .0 @iN fl-C1 0.1 100 I COO-CH (14) EXAMPLE 7 n-cr @i 3 1)v 38 g (0.2 mole) of 2-(N-methylsulfonyl)- aminophenol were partially dissolved in ml of dry acetonitrile, 17 g (0.405 mole) of dry sodium fluoride were added and 30 g (0.22 mole) of perfluoroazapropene were slowly introduced into this suspension at room temperature, while stirring. In the course thereof,

the starting material dissolved. After the introduction had been completed, the mixturewas stirred foraboiit. a further 15 minutes and filtered, and the solventiwa's concentrated in vacuo. The crude product was recrystallized from methanol. 36 g of 2-trifluoromethyli'm'i no- \=NCF 0.1 99 3 0.01 so 3-methylsulfonyl benzoxazoline were obtained as colorless crystals of melting point l42l46C. The yield of pure material was 64 percent of theory.

EXAMPLE 8 o (I =u-cr- N I (IO-CH 15 g (0.1 mole),of 2-(N-acetylamino)-phenol in 100 ml of dry acetonitrile and 9 g (0.214 mole) of dry sodium fluoride were heated to 7580C while stirring and 15 g (0.11 mole) of perfluoroazapropene were slowly passed into this suspension. After completion of 1 the reaction, themixture was filtered, the solvent was concentrated and the residue was recrystallized from chloroform. 15 g of 2-trifluoromethylimino-3-acetylbenzoxazoline were obtained as pale yellow prisms of melting point 143C. The yield of pure material was 67 percent of theory.

EXAMPLE 9 24 g (0.1 mole) of 2-N-(n-butylaminocarbonyl)-4- nitroaminophenol were dissolved in 70 ml of dry dimethylformamide, 8 g (0.19 mole) of dry sodium fluoride were added and 15 g (0.1 1 mole) of perfluoroaza propene were slowly introduced at room temperature, while stirring. After completion of the reaction, the mixture was filtered and ice water was carefully added to the reaction solution, while stirring, until no further product precipitated. The precipitate which had formed was filtered off and recrystallized from isopropanol. 21 g of 2-trifluoromethylimino-3-(nbutylaminocarbonyl)-5-nitro-benzoxazoline were obtained as colorless crystals of melting point l2l-l22 C. The yield of pure material was 61 percent of theory.

,20 EXAMPLE,

l7' g (0.1 'mole")" of 4-tert;-butyl-pyrocatechol were dissolved in 100 ml of dry toluene, 9 g (0.214 mole) of dry sodium fluoride were added and 15 g (0.11 mole) ,of perfiuoroazapropene were slowly introduced into this suspension at room temperature, while .stirring.

EXAMPLE '1 l 1 The compounds listed below were prepared by methods analogous to those of the above Examples 7 to 10.

Formula. Melting 0 Appearance point in C 56-58 col r 1 'ss 0 e Q 3 crystals c1 1 a Cl 0 colorless -NCF 3 112-115 crystals C1 0 C1 S /--NCF yellow 5 55-60 crystals NCF 3 =NCF. 5 114-116 red needles 3; 9) I brown jg; crystals Formula Melting point in 3 CO-GH 168 (decom 0811;. ion

y als pale y llow rystals colorl g y rystals y llow crystal;

Other compounds which can be similarly prepared include:

2-trifluoromethylimino-benzthioxol 2-trifluoromethylimino-3-ethanesulfonylbenzoxazoline 2-trifluoromethylimino-3-ethyl-S-bromobenzoxazoline 2-trifluoromethylimino-3-cyclohexyl-6- trifluoromethyl-benzoxazoline 2-trifluoromethylimino-3-phenyl-4-isopropoxybenzoxazoline Z-trifluoromethylimino-3-(4'-chlorophenyl)-5-diethylaminobenzoxazoline 2-trifluoromethylimino-3-(4'-methylphenyl)-5- acetylbenzoxazoline 2-trifluoromethylimino-3-( 3 '-ethoxyphenyl )-6-sulfobenzoxazoline 2-trifluoromethylimino-3-carbonamido-7- sulfonamido-benzoxazoline 2-trifluoromethylimino-3-anilidocarbonyl-6- dimethylamidosulfonyl-benzoxazoline and the like.

The following example illustrate the synthesis of a starting product of the general formula (II):

144 g 1 mole) of 4-chloro-2-aminophenol (technical product) were dissolved in 300 ml of acetone and simultaneously at a temperature of 5 to +C 80 g (1 mole) pyridine and 140 g (1 mole) chloro-formic acid i-butyl ester were added dropwise within 1 hour, while stirring. After the addition has been completed, the mixture was stirred at room temperature for about a further 30 minutes and subsequently poured with stirring into 1.5 l of water. The precipitate has been filtered with suction and dried. 240 g of 4-chloro-2-(N- carbonyl-l-butoxy)-aminophenol were obtained as light brown crystals of melting point 1 l8l22C. The Yield was 98 percent of theory. (The product thus obtained as described is the starting material for compound (25)).

It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation and that various modifications and changes may be made without departing from the spirit and scope of the present invention.

What is claimed is:

l. A 2-trifluoromethylimino-benzo-heterocyclic compound with five-members in the heterocyclic ring of the formula X I @iw 4v-cr l R in which X is oxygen or sulfur,

R is methyl, ethyl, cyclohexyl, phenyl, chlorophenyl,

nitrophenyl, lower alkylcarbo-lower alkoxy, methanesulfonyl, ethanesulfonyl, p-toluenesulfonyl, dimethylamidosulfonyl, or CO-R,

R is alkyl or alkoxy with up to 8 carbon atoms, phenyl, lower alkylamino or di-lower alkylamino.

each Z independently is halogen. trifluoromethyl. ni-

tro, lower alkyl, sulfonic acid, sulfonic acid amide. or sulfonic acid amide substituted by alkyl with up to 6 carbon atoms, and

m is an integer from O to 2.

2. A compound according to claim I in which Z is chlorine, trifluoromethyl, nitro, lower alkyl. SO H. SO2NH2, 0r SOgN(CH )2.

3. A compound according to claim 1 in which said 5 compound is 2-trifluoromethylimino-3-methylsulfonylbenzoxazoline of the formula 4. A compound according to claim 1 in which said compound is 2-trifluoromethylimino-3-carboethoxy- 4,6-dichloro-benzoxazoline of the formula =NCF N C1 C 5. A compound according to claim 1 in which said compound is 2-trifluoromethylimino-3-acetyl-5- chlorobenzoxazoline of the formula carboisobutoxy-S-chlorobenzoxazolineof the formula a *NCF 7. A compound according to claim 1 in which said compound is 2-trifluoromethylimino-3-propionylbenzoxazoline of the formula 

1. A 2-TRIFLUOROMETHYLIMINO-BENZO-HETEROCYCLIC COMPOUND WITH FIVE-MEMBERS IN THE HETEROCYCLIC RING OF THE FORMULA
 2. A compound according to claim 1 in which Z is chlorine, trifluoromethyl, nitro, lower alkyl, -SO3H, -SO2NH2, -SO2NHCH3 or -SO2N(CH3)2.
 3. A compound according to claim 1 in which said compound is 2-trifluoromethylimino-3-methylsulfonyl-benzoxazoline of the formula
 4. A compound according to claim 1 in which said compound is 2-trifluoromethylimino-3-carboethoxy-4,6-dichloro-benzoxazoline of the formula
 5. A compound according to claim 1 in which said compound is 2-trifluoromethylimino-3-acetyl-5-chlorobenzoxazoline of the formula
 6. A compound according to claim 1 in which said compound is 2-trifluoromethylimino-3-carboisobutoxy-5-chlorobenzoxazoline of the formula
 7. A compound according to claim 1 in which said compound is 2-trifluoromethylimino-3-propionyl-benzoxazoline of the formula 